Bioaccumulation and Trophic Transfer of Short Chain Chlorinated

Article pubs.acs.org/est

Bioaccumulation and Trophic Transfer of Short Chain Chlorinated Paraffins in a Marine Food Web from Liaodong Bay, North China Xindong Ma,†,‡,§ Haijun Zhang,† Zhen Wang,§ Ziwei Yao,§ Jingwen Chen,*,‡ and Jiping Chen*,† †

Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, Liaoning, China § State Oceanic Administration Key Laboratory for Ecological Environment in Coastal Areas, National Marine Environmental Monitoring Center, Dalian 116023, Liaoning, China ‡

S Supporting Information *

ABSTRACT: Short chain chlorinated paraffins (SCCPs) are under the evaluation for inclusion into the Stockholm Convention on persistent organic pollutants. However, information on their bioconcentration and biomagnification in marine ecosystems is unavailable, limiting the evaluation of their ecological risks. In this study, seawater, sediment, zooplankton, invertebrates, and fishes collected from Liaodong Bay, Bohai Sea, North China were analyzed to investigate the residual level, congener group profile, bioaccumulation, and trophic transfer of SCCPs in a marine food web. The total concentrations of SCCPs ranged from 4.1 to 13.1 ng L−1 in seawater, 65 to 541 ng g−1 (dw) in sediment, and 86 to 4400 ng g−1 (ww) in organisms. Correspondence analysis indicated the relative enrichment of C10Cl5 and C11Cl5 formula groups in most aquatic organisms. Both the logarithm bioaccumulation factors (log BAFs: 4.1−6.7) and biota−sediment accumulation factors (BSAFs: 0.1−7.3) of individual congeners implied the bioaccumulation of SCCPs. The trophic magnification factor (TMF) of ∑SCCPs was determined to be 2.38 in the zooplankton−shrimp−fish food web, indicating biomagnification potential of SCCPs in the marine ecosystem. The TMF values of individual congener groups significantly correlated with their log KOW values.

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INTRODUCTION Short chain chlorinated paraffins (SCCPs), also known as polychlorinated n-alkanes, with the carbon chain length of 10 to 13 (chlorine contents: 30% to 70% by mass), have been increasingly detected in the environment.1−3 They have been extensively used in metal-working lubricants, paints, sealants, adhesives, flame retardants, leather treatment chemicals, plasticizers in rubbers and polymers as industrial mixtures.3−5 As a candidate for inclusion into the Stockholm Convention on Persistent Organic Pollutants (POPs),14 SCCPs have attracted extensive concern worldwide due to their persistence,6 toxicological properties to aquatic organisms,7,8 bioaccumulation,9−12 and potential for long-range atmospheric transport.13 They have also been placed on toxics release inventory (TRI) in the European Union, Japan, and Canada and classified as priority toxic substances in the United States.14 China is the largest chlorinated paraffins producer in the world,5 and the production volume increased in recent years, up to 1000 kt in 2009.15 Limited studies have indicated an extensive contamination of SCCPs in different environmental matrices in China, such as sediment,16,17 soil,18 organisms,19 and air.20 Chen et al.15 found that the concentrations of SCCPs varied from 320 ng g−1 dry weight (dw) to 6600 ng g−1 dw in sediments from Pearl River Delta of South China, which © 2014 American Chemical Society

significantly exceed those reported from Europe and North America.2,4,6 Li et al.20 also found that the atmospheric levels of SCCPs (average: 137 ng m−3) in China were significantly greater than those in Japan and South Korea. It is therefore important to investigate the potential ecological and health risks of SCCPs in China. Because of the high lipophilicity (log KOW: 4.8−8.1) and resistance to metabolism,21 SCCPs have the potential to bioaccumulate in aquatic biota, which was supported by some monitoring data in organisms at different trophic levels.9,19,22,23 For example, Reth et al.23 found that SCCP concentrations in liver and cod of Arctic char and seabirds from the European arctic area ranged from 5 to 88 ng g−1 wet weight (ww). Yuan et al.19 pointed out that SCCP concentrations in mollusks from the coastal waters of Bohai Sea were up to 5510 ng g−1 dw. Nevertheless, information on bioconcentration and bioaccumulation factors of SCCPs was rarely provided.24 A few studies also focused on the biomagnifications of SCCPs in aquatic food webs. Houde et al.9 indicated that some SCCP isomers had the Received: Revised: Accepted: Published: 5964

February April 13, April 18, April 18,

23, 2014 2014 2014 2014

dx.doi.org/10.1021/es500940p | Environ. Sci. Technol. 2014, 48, 5964−5971

5965

20.0 22.1 10.3 21.0 35.3 22.2 35.4 38.7

3 3 3 3 3 3 3 3

3.1 6.2 3.1 5.1 14.6 10.8 11.3 14.8

0.5b 1.2 0.5 1.5 1.0 2 0.8 0.9

± ± ± ± ± ± ± ±

± ± ± ± ± ± ± ±

2.5 7.5 2.7 6.5 7.3 7.5 6.0 5.1

1 3 3 3 3 3 3 3 3

10 10

n

2.96 3.02 3.08 3.10 3.29 3.64 3.91 3.94

1.94 2.00 2.09 2.13 2.64 2.98 3.03 3.13 3.41 ± ± ± ± ± ± ± ±

± ± ± ± ± ± ± ± 0.52 0.18 0.28 0.32 0.41 0.35 0.38 0.34

0.26 0.35 0.35 0.29 0.30 0.31 0.31 0.28

trophic level

4.1 65

4.4 4.6 4.6 7.3 5.0 3.1 8.8 4.6

5.8 4.2 4.3 3.7 2.4 2.6 5.3 3.8 4.3 ± ± ± ± ± ± ± ±

± ± ± ± ± ± ± ± 0.2 0.2 0.2 0.1 0.1 0.1 0.3 0.2

0.2 0.2 0.2 0.3 0.2 0.1 0.2 0.2

lipid (%)

min

428 ± 269 922 ± 496 613 ± 374 1019 ± 634 691 ± 289 778 ± 437 2896 ± 1504 1186 ± 622

4.3 ± 2.7 4.4 ± 2.4 4.7 ± 2.9 8.5 ± 5.3 7.7 ± 3.2 5.1 ± 2.9 17.0 ± 8.8 7.9 ± 4.1

5.6 11.9 ± 4.9 5.9 ± 2.4 8.7 ± 3.5 1.6 ± 1.0 2.7 ± 1.2 6.6 ± 3.1 4.0 ± 2.6 6.3 ± 3.6

∑SCCPs (ng g−1,dw)

∑SCCPs (ng g−1,ww) 280 2259 ± 934 1058 ± 429 1217 ± 484 3264 ± 219 510 ± 227 1053 ± 497 243 ± 156 502 ± 288

7.7 299

arithmetic mean

13.1 541

max

9.7 ± 6.1 20.1 ± 10.8 13.3 ± 8.1 13.9 ± 8.7 13.9 ± 5.8 25.5 ± 14.3 32.9 ± 17.1 25.8 ± 13.5

4.8 54.1 ± 22.4 24.5 ± 10.0 32.8 ± 13.0 13.9 ± 9.3 19.3 ± 8.6 19.8 ± 9.3 6.4 ± 4.1 11.6 ± 6.7

TOC (%)

4.7 5.1 4.9 5.1 5 5 5.6 5.2

4.5 5.5 5.1 5.2 4.6 4.8 5.1 4.6 4.8

2.3 1 1.4 0.6 0.8 0.8 0.3 0.5

BSAFc (lw TOC−1)

23.6 ± 13.4

∑SCCPs (μg·gOC−1)

Log BAFc (L kg−1 ww)

1.26 ± 0.57a

∑SCCPs (μg g−1,lw)

2.6 182

SD

Average ± standard deviation. bRP, short necked clam (Ruditapes philippinarum); AI, Chinese scallop (Chlamysfarreri); MV, Mactra Quadrangularis (Mactra veneriformis,Reeue); HT, Conch Neptunea (Hemif usus tuba); RVP, rock shell (Rapanavenosa peichiliensis); SS, Samoan crab (Scylla serrata); PC, Chinese shrimp (Penaeuschinensis); SC, Coastal mud shrimp (Solenoceracrassicornis); LH, redeye mullet (Liza hematocheila); SH, goby (Synechogobius hasta); TK, China anchovy (Thrissakammalensis); CS, half-smooth tongue-sole (Cynoglossussemilaevis); PI, flathead fish (Platycephalusindicus); NA, spotted maigre (Nibeaalbif lora); LJ, black spotfed bass (Lateolabraxjaponicus); SN, spanish mackerel (Scomberomorusniphonius). cBAF and BSAF of ∑SCCPs were both the averages.

a

Invertebrates ZK RP AI MV HT RVP SS PC SC Fishes LH SH TK CS PI NA LJ SN

Water (ng L ) Sediment (ng g−1 dw) Organism speciesb n length (cm)

−1

matrix

∑SCCPs

Table 1. Parameters and ∑SCCPs in Water, Sediment, and Organism in Liaodong Bay, North China

Environmental Science & Technology Article


Environmental Science & Technology

Article

were extracted with a mixture of acetone and hexane (v:v = 1:1) by an Accelerated Solvent Extractor (ASE 350, Dionex USA). A 10.0 μL recovery standard of 13C6-HCB was added prior to extraction. After extraction, 2.0 g of activated copper powder was added into the concentrated sediment extract (about 5 mL) to remove elemental sulfur by shocking, and about 30 g of acid silica gel (30% concentrated sulfuric acid, w/w) was added into the organism extract to remove lipids and other interferences. Finally the extracts were concentrated to 2.0 mL for further cleanup. All concentrated eluents and extracts were further cleaned by a multilayer column (10 mm i.d.) which consisted of 5.0 g of activated alumina, 2.0 g of basic silica gel, 2.0 g of activated silica gel, 5.0 g of acid silica gel (30%, w/w), and 4.0 g of anhydrous Na2SO4 from the bottom to top. The extract was eluted with 80 mL of hexane (fraction 1) and 120 mL of hexane/DCM (1:1, v/v) (fraction 2). The first fraction was discarded, and the second fraction was collected and concentrated to about 50 μL under a gentle N2 stream. A 10.0 μL internal standard of 13C6-HCH (100 ng mL−1) was added and mixed completely prior to instrumental analysis. The instrumental analysis was performed on a gas chromatograph coupled with a triple quadrupole mass spectrometer at electron capture negative ion mode (Agilent 6890A/5973iECNI, Agilent Co. Ltd., USA). The quantification of total SCCPs was conducted using the procedure described by Reth et al.,27 and congener group abundance profiles were generated from the actual relative integrated signals corrected by isotopic abundance and response factors.28 Potential interference from middle chain chlorinated paraffins (MCCPs, carbon chain length of 14 to 17) was monitored according to the method described by Zeng et al.18 A total number of 24 SCCP congeners with the carbon chain length of 10 to 13 and the chlorine number of 5 to 10 were analyzed. Detailed materials, standards and reagents, instrumental conditions, and quantitative procedure are listed in the Supporting Information (SI). Quality Assurance and Quality Control. Strict quality controls were implemented to ensure the correct identification and accurate quantification of the target compounds. All equipment were thoroughly rinsed with dichloromethane before experiment, and the sample preparations were conducted in a super clean lab to avoid background contamination. One method blank sample was included in each batch of 10 samples to monitor the contamination, and the results showed all targeted SCCPs in blanks were below or close to the detection limits. The result of blank spiking experiment indicated that both the relative standard deviation of the recovery and repeatability tests were less than 15%. The method detection limit (MDL) for total SCCPs was calculated by tripling the standard deviation of the background signals from eight blank samples (n = 8). The MDLs of seawater, sediment, and organism were estimated to about 1.2 ng L−1, 20 ng g−1, and 60 ng g−1, respectively. The surrogate recoveries of 13 C6-HCB in all samples ranged from 76.5% to 97.4%. The final concentrations of SCCPs reported in this study were not blank corrected. Parameter Measurement and Statistical Analysis. Total organic carbon (TOC) was measured by the high temperature combustion method using total organic carbon analyzer (Vario TOC cube, Elementar Co. Ltd., GER). Lipid content (synchronously extracted by hexane and acetone from samples) was determined gravimetrically. Detailed analysis of stable nitrogen isotope and calculations of trophic levels (TL)

potential to biomagnify in aquatic food webs from the freshwater of Lake Ontario and Lake Michigan (including invertebrates and fishes). Zeng et al.22 also revealed that SCCPs could be slightly biomagnified in fresh aquatic food web (including plankton, fish and turtle) near a municipal sewage treatment plant. However, available data about the bioaccumulation and biomagnification of SCCPs, especially in marine food web, is still limited. Bohai Sea is a large semienclosed inner sea with a narrow strait to the Yellow Sea, and the half-exchange time of seawater in Liaodong Bay was estimated to be about 3 years.25 The poor seawater exchange and the accelerated industrialization of the cities around Liaodong Bay would inevitably result in a considerable contamination of pollutants in aquatic environment of the Bay. It provides a representative marine ecosystem influenced by the estuary to investigate the environmental behavior of SCCPs. In addition, our previous studies have indicated that the sediments and soils from the upstream of Liao River and marine sediments from the mouth of Liao River presented the high contamination.16,26 Hence, in this study, seawater, marine sediments, and organisms at different trophic levels (including zooplankton, invertebrates, and fishes) were collected and analyzed to investigate the residual level, congener group specific distribution, and transfer behavior of SCCPs. This study was expected to evaluate the bioaccumulation and biomagnification of SCCPs in the marine ecosystem and to provide a better understanding about the influence of biological and physicochemical factors (such as KOW) on bioaccumulation and trophic transfer of SCCPs.

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EXPERIMENTAL SECTION Sampling Sites and Sample Collection. Ten seawater samples, ten marine sediments, and 49 aquatic biological samples were collected from Liaodong Bay. Aquatic organisms included zooplankton, eight benthic invertebrate species (three bivalve species, two conch species, two shrimp species, and one crab species) and eight fish species (Table 1). Zooplankton, mainly consisting of Mysidacea, Cladocera, and Coelenterata, was collected by vertical trawl of small ring net (diameter 320 mm) with 0.096 mm mesh. Invertebrates and fishes were caught with a bottom trawl. Detailed spatial information for the sampling sites is given in Figure S1. All collected samples were wrapped in aluminum foil and transported with ice to laboratory after being sealed in PTFE plastic bags. The length and weight of collected invertebrate and fish species were first measured, and then soft tissues of invertebrate and muscles of fish were dissected. The whole zooplankton, dissected soft tissues and muscles together with sediments were lyophilized, ground, homogenized, and stored in precleaned brown glass bottles at −20 °C until analysis. Sample Preparation, Instrumental and Quantitative Analysis. Dissolved SCCPs were separated and enriched from 10.0 L seawater sample using the solid-phase extraction method. The seawater was spiked with a 10.0 μL recovery standard of 13C6-HCB (100 ng mL−1) and then filtered by a glass fiber membrane (1.0 μm pore size, 47 mm diameter). Then the filtered seawater was passed through a solid-phase membrane disk (3 M Empore C18, 47 mm, 3 M Co., USA) under a constant negative pressure of 0.2−0.4 atm. Finally, the membrane disk was successively eluted with 15 mL of hexane and 30 mL of dichloromethane (DCM), and the eluents were combined and concentrated to 2.0 mL for further cleanup. SCCPs in dry sediment (10.0 g) and biota sample (15.0 g) 5966



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Figure 1. Congener group abundance profiles of SCCPs in seawater (mean), sediments (mean), and organisms.

zooplankton (ZK) and Chinese scallop (AI), respectively. The lipid normalized ΣSCCPs between different biota groups varied largely, and the descending mean values followed the sequence of bivalves (37.1 μg g−1 lw) > crabs (19.8 μg g−1 lw) ≈ fishes (19.4 μg g−1 lw) > conches (16.6 μg g−1 lw) > shrimps (9.0 μg g−1 lw) > zooplankton (4.8 μg g−1 lw). Similarly, the lipid contents also varied largely according to the aquatic species. However, a significant relationship between ΣSCCPs and lipid contents (R2 = 0.46, p < 0.05, Figure S3) was observed, indicating lipid content is an important factor influencing SCCP bioaccumulation in aquatic species. Compared with other reports, the ΣSCCPs in bivalves were comparable to those from the other areas around Bohai Sea (64.9−5510 ng g−1 dw).19 The ΣSCCPs in fishes were generally 1 order of magnitude higher than those from the North and Baltic Sea (19−286 ng g−1 ww)27 and the Mediterranean and Atlantic ocean (0.25−1.22 μg g−1 lw),31 while comparable to those detected in freshwater from industrialized areas of England and Wales ( scallops (1.0) > crabs (0.8) > conches (0.7) > shrimps (0.4). The values of clams and scallops were similar to that of the bivalves collected from this area (1.1 for Cyclina sinensis, 1.3 for Ruditapes philippinarum, and 1.6 for Mactra veneriformis).33 The variation of BSAFs is most likely a result of differences in lipid composition, metabolism, and selective excretion abilities between different species.32 The BSAF values of SCCP formula groups were also calculated according to the ratio of their relative abundances in organism and sediment (see the SI), and the results of major SCCP formula groups ranged from 0.1 to 7.3 (average: 1.2, Table S2). These data were comparable to other POPs reported, for example PCBs in bottom fishes (0.01−5.0)34 and HCHs in sediment-dwelling animals (0.81−2.34),35 but generally lower than those of DDTs (1.1−27.9)35 and PBDEs in Mytilus edulis (1.0−11.4).36 The BSAFs of individual SCCP formula groups generally presented a decreasing tendency with the increase of carbon chain length, chlorine contents, and KOW values, except short necked clam (RP) and rock shell (RVP) (Table S2, Figure S6). This result was obviously opposite to the trend of BAFs and implied the discrepancy of bioaccumulation between organism−water system and organism−sediment system. One explanation might be that the highly chlorinated SCCPs are more strongly adsorbed to the organic matter in sediment which makes them less bioavailable.32 Another one might be the different membrane permeability of SCCPs congener, i.e. the higher chlorinated congeners with high molecular weight have lower penetration ability into organism.36 Trophic Magnification Factors (TMFs). TMF values are estimated as the antilog of the regression slope (b) with base 10 (TMF = 10b) of the linear regression between logarithm SCCP concentrations (lipid equivalent) and TL values of aquatic species,37 and the detailed calculation of TMF is listed in the SI. Statistical analysis indicated that there were no significant linear correlations (P > 0.05) between the TL values and lipidnormalized concentrations of ∑SCCPs, and SCCP formula groups in the all aquatic species (Table S3). As mentioned above, the bivalve species had higher lipid-normalized concentrations of SCCPs (Table 1), and the inclusion of

Figure 2. Scatter plots of two dimensions conducted by correspondence analysis between SCCP congener groups and test samples. RP, short necked clam; RVP, rock shell.

dimension 1, while seawater and sediment could be discriminated by dimensions 1 and 2. Seawater samples all had negative scores on the two dimensions, resulting from the relatively high contents of lower chlorinated congener groups, C12Cl5, C12Cl6, C13Cl5, and C13Cl6. Sediments had positive scores on dimension 2, which was mainly due to the higher contents of highly chlorinated C13-CPs (Cl7−Cl9). Except for two kinds of bivalve species, short necked clam (PR) and rock shell (RVP), aquatic organisms had higher contents of C10Cl5 and C11Cl5 formula groups compared to sediment, and thus they were classified into one group. Bioaccumulation Factors (BAFs) between Seawater and Organisms. BAF was calculated by the ratio of average SCCP concentration in aquatic organism on wet weight basis (Co) to average dissolved SCCP concentration in filtered seawater (Cs), i.e., BAF = Co/Cs. However, in this study, it should be acknowledged that using a one-time sampling concentration to reflect a time-weighted average concentration was a limitation in the calculation of BAF. As shown in Table 1, the logarithm BAFs of ∑SCCPs ranged from 4.5 to 5.6 for all organisms, and these values obviously varied according to the aquatic species. Zooplankton had the lowest BAF value, which might reflect their uncertain exposure to SCCPs in seawater due to their living habits with a relatively strong flowability.32 The logarithm BAFs of ∑SCCPs for fish were in the range of 4.7−5.6 with an average value of 5.1, and this result was lower than that reported from the Ontario Lake (6.0−6.6).9 The arthropod shrimps with the log BAFs of 4.6 (PC) and 4.8 (SC) showed the relatively lower bioaccumulation compared with most fishes. It was noticeable that the bivalve species, short necked clam (RP, 5.5), Chinese scallop (AI, 5.1), and Mactra quadrangularis (MV, 5.2), all had the higher BAF values for ∑SCCPs. This phenomenon might be due to the relatively high concentration of SCCPs in the underlying interstitial water because of their closeness to sediment.22 Another possible reason might be due to the lower elimination rate of SCCPs in these bivalve species.12,32 To investigate the effect of chemical properties of SCCPs on their bioaccumulation, the BAF value of individual SCCP formula group was calculated according to the ratio of their relative abundances in organism and seawater. The detailed calculation method and calculated results are shown in the SI. The BAFs of SCCP formula groups for all organisms ranged 5968



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lower than those of PBDEs (2.60−7.24)40 and coplanar PCBs (3.40−12.26),41 but higher than those of PAHs (0.11−0.45),39 4-nonylphenol and nonylphenol ethoxylates (0.45 and 1.15),42 and MCCPs (0.14−0.29).9 As shown in Figure 4, an increasing tendency of TMFs with the increase of carbon chain length was observed, and Cl8 and Cl9 homologues exhibited the highest TMFs. In addition, the significant correlation between TMFs of SCCP formula groups and their log KOW values (R2 = 0.43, p < 0.01, Figure 4) implied that KOW is a major governing factor for congener specific biomagnification of SCCPs.43 The present work showed that SCCPs are widely distributed in water, sediment, and organisms in the marine aquatic ecosystem of Liaodong Bay. The high-level bioaccumulation of SCCPs in the organisms facilitated the observation of the biomagnification potential, and the TMF > 1 indicated the trophic transfer potential of SCCPs in the marine ecosystem. However, TMF can be influenced by interspecies ecological (e.g., the uncertainty of food intake)32 and organismal parameters such as metabolism, reproductive status, migration, and age, particularly among fish species.44,45 Liaodong Bay is semienclosed and the caught fish all reside in the offshore environment, and thus the effect of fish migration on the biomagnification of SCCPs could be neglected. Meanwhile, the effect of age could also be alleviated because the samples consisted of mixtures of subsamples with different ages from different locations. Hence, the significant variation in TMF values for different SCCP congener groups should mainly be the result from the differences in their absorption and metabolism in organisms.32,45,46 Further work is needed to study the factors affecting the biomagnification of SCCPs such as intake rate, degradation, and transformation in vivo, etc., and thereby to evaluate the ecological risks of SCCPs to the marine aquatic ecosystem.

these three bivalve species seriously distorted the general relationship for SCCPs (Figure 3). According to the predator−

Figure 3. Relationship between trophic level (TL) and lipidnormalized concentrations (lw) of ΣSCCPs.

prey relationship of this marine ecosystem, the collected fishes mainly prey the shrimps, smaller-size fishes, and zooplankton.38 Some smaller-size bivalves, conches, and crabs can also occasionally become prey to the fishes, but the pollutants in these species are not easily released via digestion.39 Therefore, these shelly benthic species were excluded, and the trophic transfer of SCCPs in food web of zooplankton−shrimp−fish (Z−S−F) was further investigated. As shown in Figure 3, a significant linear correlation (P < 0.01) between the TL values and lipid-normalized concentrations of ∑SCCPs in the food web Z−S−F was observed, and the TMF value was calculated to be 2.38. The result indicated that SCCPs had the potential to biomagnify in marine food web. The observed TMF of ∑SCCPs was generally higher than those from the freshwater food webs of Lake Gaobeidian (1.61)22 and Lake Michigan (1.2).9 To further investigate congener specific biomagnification of SCCPs, TMF values for SCCP formula groups were calculated (Table S3). Significant linear correlations were found between the TL values and lipid-normalized concentrations for most SCCP formula groups, except C10Cl6, C11Cl7, C12Cl7, and C13Cl7, and the calculated TMFs ranged from 1.45 to 5.65. Compared with other organic pollutants in the same and similar food webs, the TMFs of SCCP formula groups were

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ASSOCIATED CONTENT

S Supporting Information *

Supplementary description on experimental section; tables on BAF, BSAF, and TMF values for individual SCCP formula groups in relation to chlorine contents and KOW values; figures on sampling sites and concentration of ∑SCCPs in water and sediment samples, SCCP congener group abundance profiles, correlation between TOC contents and ∑SCCPs in sediments, correlation between lipid contents and ∑SCCPs in organisms, correlations of log BAFs and BSAFs with the numbers of

Figure 4. Relationships of TMFs of SCCP congener groups with the number of carbon atoms (NC, left) and the log KOW values (right). 5969



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(13) Tomy, G. T.; Stern, G. A.; Lockhart, W. L.; Muir, D. C. G. Occurrence of C10−C13 polychlorinated n-alkanes in Canadian midlatitude and arctic lake sediments. Environ. Sci. Technol. 1999, 33 (17), 2858−2863. (14) Persistent Organic Pollutants Review Committee. Supporting document for the draft risk profile on short-chained chlorinated paraffins. UNEP/POPS/POPRC.6/INF/15. Stockholm Convention on Persistent Organic Pollutants, Ed. Geneva, 2010. (15) Chen, M.; Luo, X.; Zhang, X.; He, M.; Chen, S.; Mai, B. Chlorinated paraffins in sediments from the Pearl River Delta, South China: spatial and temporal distributions and implication for processes. Environ. Sci. Technol. 2011, 45, 9936−9943. (16) Gao, Y.; Zhang, H. J.; Su, F.; Tian, Y. Z.; Chen, J. P. Environmental occurrence and distribution of Short Chain Chlorinated Paraffins in sediments and soils from the Liaohe River Basin, P. R. China. Environ. Sci. Technol. 2012, 46, 3771−3772. (17) Zeng, L. X.; Zhao, Z. S.; Li, H. J.; Wang, Th.; Liu, Q.; Xiao, K.; Du, Y. G.; Wang, Y. W.; Jiang, G. B. Distribution of Short Chain Chlorinated Paraffins in Marine Sediments of the East China Sea: Influencing Factors, Transport and Implications. Environ. Sci. Technol. 2012, 46, 9898−9906. (18) Zeng, L. X.; Wang, Th.; Han, W. Y.; Yuan, B.; Liu, Q.; Wang, Y. W.; Jiang, G. B. Spatial and vertical distribution of short chain chlorinated paraffins in soils from waste water irrigated farmlands. Environ. Sci. Technol. 2011, 45, 2100−2106. (19) Yuan, B.; Wang, Th.; Zhu, N. L.; Zhang, K. G.; Zeng, L. X.; Fu, J. J.; Wang, Y. W.; Jiang, G. B. Short Chain Chlorinated Paraffins in mollusks from coastal waters in the Chinese Bohai Sea. Environ. Sci. Technol. 2012, 46, 6489−6491. (20) Li, Q. L.; Li, J.; Wang, Y.; Pan, X. H.; Zhang, G.; Luo, C. L.; Kobara, Y.; Nam, J. J.; Jones, K. C. Atmospheric short-chain chlorinated paraffins in China, Japan, and South Korea. Environ. Sci. Technol. 2012, 46, 11948−11954. (21) Fisk, A. T.; Tomy, G. T.; Cymbalisty, C. D.; Muir, D. C. G. Dietary accumulation and quantitative structure−activity relationships for depuration and biotransformation of short (C10), medium (C14),and long (C18) carbon-chain polychlorinated alkanes by juvenile rainbow trout (Oncorhynchusmykiss). Environ. Toxicol. Chem. 2000, 19 (6), 1508−1516. (22) Zeng, L. X.; Wang, Th.; Wang, P.; Li, Q.; Han, S. L.; Yuan, B.; Zhu, N. L.; Wang, Y. W.; Jiang, G. B. Distribution and trophic transfer of Short-Chain Chlorinated Paraffins in an aquatic ecosystem receiving effluents from a sewage treatment plant. Environ. Sci. Technol. 2011, 45, 5529−5535. (23) Reth, M.; Ciric, A.; Christensen, G. N.; Heimstad, E. S.; Oehme, M. Short- and medium-chain chlorinated paraffins in biota from the European Arctic-differences in homologue group patterns. Sci. Total Environ. 2006, 367, 252−260. (24) United Nations Environment Programme (UNEP). Draft risk profile: short-chained chlorinated paraffins. UNEP/ POPS/POPRC.3/ 16, Geneva, 19−23 November 2007. (25) Wei, H.; Tian, T.; Zhou, F.; Zhao, L. Numerical study on the water exchange of the Bohai Sea: simulation of the half-life time by dispersion model. J. Ocean Univ. Qingdao 2002, 32, 519−525. (26) Gao, Y.; Wang, C.; Zhang, H. J.; Zou, L. L.; Tian, Y. Z.; Chen, J. P. Analysis of short-chain chlorinated paraffins in sediment samples from the mouth of the Daliao river by HRGC/ECNI-LRMS. Environ. Sci. 2010, 31, 1904−1908 (in Chinese). (27) Reth, M.; Zencak, Z.; Oehme, M. New quantification procedure for the analysis of chlorinated paraffins using electron capture negative ionization mass spectrometry. J. Chromatogr. A 2005, 1081, 225−231. (28) Tomy, G. T.; Stern, G. A.; Muir, D. C. G.; Fisk, A. T.; Cymbalisty, C. D.; Westmore, J. B. Quantifying C10−C13 polychloroalkanes in environmental samples by high-resolution gas chromatography/electron capture negative ion/ high-resolution mass spectrometry. Anal. Chem. 1997, 69, 2762−2771. (29) Nicholls, C. R.; Allchin, C. R.; Law, R. J. Levels of short and medium chain length polychlorinated n-alkanes in environmental

carbons and chlorines. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Authors

*Phone/Fax: +86 411-8470-6269. E-mail: [email protected] (Jingwen Chen). *Phone/Fax: +86 411-8437-9562. E-mail: [email protected] (Jiping Chen). Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors thank the Natural Science Foundation of China (Grant No. 41201491, 21077102, and 21337002) and the Chinese Public Welfare Projects on Environmental Protection (201105013 and 201309030).

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REFERENCES

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